JP2006216563A - Method of manufacturing organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a patterned organic electroluminescent element. <P>SOLUTION: The method uses a donor film for thin film transfer having a flexible polymer film layer. Thereby, since the thin film can be transferred even with less energy and a plurality of layers can be transferred at once, an efficiently patterned organic electroluminescent element can be manufactured. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for manufacturing a patterned organic electroluminescence (EL) device, and more specifically, using a donor film for thin film transfer including a soft polymer film layer, The present invention relates to a method of manufacturing a patterned organic EL device by transferring an organic layer and a metal layer from an upper donor layer to a lower acceptor layer by one or more of heat, electric energy, and pressure.

  An organic EL device is a self-luminous device that utilizes the phenomenon of generating light by passing an electric current through a fluorescent or phosphorescent organic layer and combining electrons and holes in the organic layer. In addition, the manufacturing process is simple, and high image quality and light viewing angle can be realized. In addition, the video can be realized perfectly, high color purity can be realized, and it has electrical characteristics suitable for portable electronic devices with low power consumption and low voltage drive. The use of the organic EL element is very diverse such as a display or a backlight unit.

  In general, an organic EL device includes an organic layer including an anode, a cathode, a hole transport layer (HTL), a light emitting layer (EML), and an electron transport layer (ETL). . Further, in order to inject holes and electrons more efficiently, a hole injection layer (HIL) is provided between the anode and the hole transport layer and between the electron transport layer and the cathode. And an electron injection layer (EIL).

  At this time, the holes injected from the anode into the light emitting layer through the hole injection layer and the hole transport layer and the electrons injected from the cathode through the electron injection layer and the electron transport layer into the light emitting layer form excitons. The exciton emits light corresponding to the energy between holes and electrons.

  The anode is selected from transparent conductive materials such as ITO (Indium Tin Oxide), IZO (Indium Tin Oxide), and ITZO (Indium Tin Zinc Oxide) having a high work function, and the cathode has a low work function. Selected from chemically stable metals.

  As a kind of organic EL element, there is a passive matrix type organic EL element, and when this element is used and a current is passed between an anode and a cathode in which an organic film composed of a plurality of layers is interposed, two electrodes cross each other. Lights at the part. At this time, the anode is formed in a predetermined pattern on the organic EL layer.

  On the other hand, it is necessary to form a fine pattern of an organic thin film such as a light emitting layer, an electron injection layer, a hole injection layer, etc. in order to achieve full color of the organic EL element.

  As a method for forming a fine pattern of an organic thin film, there is a lithography method in which an organic thin film is finely processed by using a photoresist pattern obtained by coating, exposing and developing a photoresist on the organic thin film. However, since the organic thin film formed by this method can be deformed by the organic solvent used in the process and the residue of the developer, it is substantially impossible to apply. Furthermore, as another method, there is a vacuum vapor deposition method using a mask, but this has a problem that it is difficult to perform microfabrication of several tens of microns or less.

  Patent Document 1 discloses a method of forming a highly patterned organic layer in a full-color organic EL element. In this method, an organic EL material capable of vapor deposition is coated on a support having a heating device. Thereafter, the light emitting material is transferred to the concave surface portion by vapor deposition on the bottom electrode of an OLED (Organic Light Emitting Diode) provided with a transistor array through an opening mask. This method is similar to thermal vapor deposition in which an organic substance is heated in a vacuum state and vapor deposition is performed through a shadow mask.

  On the other hand, a patterning method using a laser transfer method is also known. Patterning using the laser transfer method requires a minimum light source, transfer film and substrate, and light emitted from the light source is absorbed by the light-to-heat conversion layer of the transfer film and converted to thermal energy. The material constituting the transfer layer of the transfer film is transferred to the substrate by energy, and a desired image is formed.

  Since the light-to-heat conversion layer must convert light incident through a laser into heat energy, a material having a large heat conversion capacity, for example, an organic compound such as carbon black or IR-pigment, a metal material such as aluminum, It consists of an oxide of a metallic material or a mixture of the aforementioned materials.

  Patent Document 2 includes a base film, a photothermal conversion layer formed on the base film, and a transfer layer formed on the photothermal conversion layer and made of a low molecular weight substance. The layer is transferred with heat by the laser, part of the transfer layer irradiated with the laser is detached from the transfer layer due to a change in adhesive force with the photothermal conversion layer, and the part not irradiated with the laser is bonded Adhesive force between the substrate of the organic EL element fixed to the light-to-heat conversion layer by force and onto which the low-molecular substance formed on the transfer layer is transferred and the low-molecular substance, and the light-to-heat conversion layer and the low molecule Since the adhesive strength with the substance is greater than the adhesive force between the low molecular weight material in the region irradiated with laser in the transfer layer and the low molecular weight material in the region not irradiated with laser, the low strength in the region irradiated with laser is low. Molecular material Disclosed is a donor film for a low-molecular full-color organic EL device that is separated from each other and has undergone mass transfer from the photothermal conversion layer to the substrate. .

  However, when the pattern is transferred by the laser transfer method, the flexibility of the upper donor film is lowered, the adhesive force with the lower acceptor film is low, and a lot of energy is required at the time of transfer. In addition, since only an organic substance can be transferred, for example, when a passive matrix type organic EL element is manufactured, there is a trouble that a step of depositing a metal after an organic layer patterning must be performed separately. Furthermore, a photothermal conversion layer is always required.

  The cold welding method disclosed in Non-Patent Document 1 is a method of removing a desired portion of a metal film coated on two different substrates after stamping with a metal-metal adhesive force, In addition to the organic layer laminated on the cathode layer, a stamp coated with a metal on the cathode layer deposited on the entire surface of the organic layer is pressed with a large pressure and then removed to form a cathode pattern. However, since a large pressure is used at this time and a metal-metal adhesive force is used, only a metal having a large work function such as Au-Au, Ag-Ag, Pd-Pd or an alloy with these other metals is used. Since it is limited and is not a transfer method but a lift-off method, it can be used only by a patterning method after the element is completed.

  On the other hand, as a cathode transfer method described in Non-Patent Document 2, an organic layer in which a SAM layer is formed as a separation promoting layer on a glass mold and an aluminum layer is formed thereon is laminated on an anode on a substrate. There is also a method of transferring the cathode by pressing the layer with a large pressure. However, in this case as well, since a glass mold is used using a large pressure, a separation promoting layer is necessarily required, and there is a risk of physical damage to the organic layer.

  On the other hand, polydimethylsiloxane (PDMS) is a kind of silicon-based elastic rubber having a low glass transition temperature, and various patterning methods such as microcontact printing, micromolding and nanotransfer printing using this as a mold are known. It has been.

In Patent Document 3, in a passive matrix type organic EL element having a light emitting region at a portion where a first electrode and a second electrode where an organic EL layer is interposed is formed, a first formed on a substrate in a first direction is disclosed. An electrode, an organic EL layer formed on the entire surface of the substrate covering the first electrode, and an upper portion of the organic EL layer, which is positioned in a second direction intersecting the first direction, and W / L = A patterned second electrode is formed by removing by a thermal transfer method using a PDMS mold having a concavo-convex portion in which a concave portion and a convex portion in which a relational expression of 0.2 to 20 and D ≧ L × 20 is satisfied is repeatedly formed. A passive matrix type organic EL device is disclosed. In the method, the patterned second electrode is formed by bonding the mold to the second electrode and then thermally curing to remove the second electrode that is bonded to the convex portion of the mold from the substrate. However, the method is the same in that the second electrode deposited on the entire surface by the cold welding method is used to remove the second electrode due to a difference in relative bonding force.
US Pat. No. 5,937,272 US Patent Publication No. 2004-0191564 Korean Patent Publication No. 2003-0073578 Kim et al., Science, vol 288, p831 (2000) Rhee and Lee, Applied Physics Letters, vol. 81, p4165, (2002)

  The technical problem to be achieved by the present invention is that adhesion between the transfer layer of the donor film and the acceptor film to be transferred is good and transfer is possible with a small amount of energy. The present invention provides a method for producing an organic EL device by using a donor film for thin film transfer that can transfer a plurality of layers such as a molecular layer at a time and does not require a photothermal conversion layer.

  In order to achieve the technical problem, in the first aspect of the present invention, a step of forming an anode on a substrate, a step of forming an organic layer on the anode, and patterning in an uneven shape on the organic layer One or more of heat, light, electricity and pressure after contacting the metal layer of the donor film for thin film transfer comprising the formed soft polymer film layer and the metal layer formed on the polymer film layer And transferring the metal layer to the organic layer to form a patterned cathode, and a method of manufacturing an organic electroluminescent device is provided.

  In the second aspect of the present invention, a step of forming an anode on a substrate, a step of forming a first organic layer on the anode, and a soft polymer patterned in a concavo-convex pattern on the first organic layer After contacting the second organic layer of the donor film for thin film transfer comprising the film layer and the second organic layer formed on the polymer film layer, one or more of heat, light, electricity and pressure are applied. Transferring the second organic layer to the first organic layer to form a patterned second organic layer; and depositing a metal layer on the patterned second organic layer to form a cathode. And a method for producing an organic electroluminescent device comprising the steps of:

  In the third aspect of the present invention, a step of forming an anode on a substrate, a step of forming a first organic layer on the anode, and a soft polymer patterned in a concavo-convex pattern on the first organic layer After contacting the second organic layer of the donor film for thin film transfer comprising the film layer, the metal layer formed on the polymer film layer, and the second organic layer formed on the metal layer, heat, light And applying at least one of electricity and pressure to transfer the metal layer and the second organic layer to the first organic layer to form a patterned second organic layer and cathode. A method for manufacturing a light emitting device is provided.

  The organic layer, the first organic layer, and the second organic layer may include a hole transport layer, a light emitting layer, and an electron transport layer.

  According to another embodiment of the present invention, the soft polymer film layer has a glass transition temperature of room temperature or lower, a silicone elastomer such as a silicone rubber such as polydimethylsiloxane (PDMS), polybutadiene, Nitrile rubber, acrylic rubber, butyl rubber, polyisoprene, styrene-butadiene copolymer and the like can be used.

  According to still another embodiment of the present invention, the soft polymer film layer may further include a support layer on a surface opposite to the patterned side.

  In the 4th aspect of this invention, the organic EL element manufactured by the said method is provided.

  According to the method for producing an organic EL element of the present invention, the metal layer and the organic layer can be transferred at a time, transfer is possible even with low energy, and the photochemical reaction of the organic layer can be prevented, so that the patterning is efficiently performed. An organic EL element can be manufactured.

  If an organic EL device is manufactured according to the present invention, a plurality of layers can be transferred at once to a metal layer and an organic material layer, and transfer is possible with a small amount of energy. Therefore, the organic EL device can be easily and efficiently patterned. Can be manufactured.

  Hereinafter, the present invention will be described in detail with reference to the drawings.

  The method for producing a patterned organic EL device according to the present invention is characterized in that a donor film for thin film transfer including a soft polymer film layer is used. The polymer film layer preferably has a thickness of 0.5 mm or more, but if it is less than 0.5 mm, the film may be too flexible and difficult to process. Further, the polymer film has a concave portion and a convex portion, and the ratio of the distance between the convex portion and the convex portion to the distance between the concave portion and the concave portion is preferably 0.1 or more, More preferably, it is 0.5 or more. If it is less than 0.1, a sagging phenomenon may occur where the surface of the upper concave portion is in close contact with the lower organic layer during mp junction with the lower organic layer. The ratio of the width to the height of the convex portion is preferably 0.2 or more, more preferably 1 or more. If it is less than 0.2, a phenomenon may occur in which the convex portion collapses without being able to withstand the pressure.

  That is, after forming an anode on a substrate, patterning a part of an organic layer formed on the anode, patterning a cathode formed on the organic layer, or part of the organic layer When both the cathode and the cathode are patterned, transfer is performed using a donor film for thin film transfer.

  The substrate may be manufactured from glass or plastic.

  At this time, the donor film for thin film transfer includes a soft polymer film layer patterned in an uneven shape having a glass transition temperature of room temperature or lower, and a metal layer, an organic layer, or a metal layer formed on the polymer film layer. Unlike the donor film used in the conventional laser induced thermal imaging (LITI), a photothermal conversion layer is not required and transfer is possible even at low energy. There are advantages.

  A soft polymer film layer having a glass transition temperature of room temperature or lower is obtained by patterning a surface on which a layer to be transferred is attached in an uneven shape. By providing the upper substrate so that there are concave and convex portions in this way, when applying energy such as light and heat to the donor film, it is necessary to scan and add as in the existing laser transfer method However, there is an advantage that patterning is possible even if light is irradiated at a time as a whole. Therefore, a large amount of transfer can be performed in a single process.

  The soft polymer film layer having a glass transition temperature of room temperature or lower is selected from the group consisting of a transparent silicone elastomer, polybutadiene, nitrile rubber, acrylic rubber, butyl rubber, polyisoprene, and styrene-butadiene copolymer. More than species, most preferably polydimethylsiloxane.

  In addition, when the glass transition temperature of the polymer constituting the polymer film layer is normal temperature or lower, conformal contact is possible when contacting the lower organic layer, and a fan generated between molecules and atoms It is preferable because it has strong Dell attractive force, excellent adhesion between the polymer film layer and the organic layer as the transfer layer, and can be easily transferred without adding much heat or light.

  First, when manufacturing an organic EL device by transferring only a cathode using a donor film for thin film transfer, a step of forming an anode on a substrate, a step of forming an organic layer on the anode, and the organic After contacting a metal layer of a donor film for thin film transfer comprising a soft polymer film layer patterned in a concavo-convex shape and a metal layer formed on the polymer film layer on the layer, heat, light, And applying one or more of electricity and pressure to transfer the metal layer to the organic layer to form a patterned cathode. In this embodiment, the metal layer may be formed not only on the convex portion of the polymer film layer but also on the concave portion.

When the energy source is light, since the entire surface can be exposed at once with an ultraviolet lamp, a large amount of transfer can be performed with a very simple operation. The irradiation time of the light to be irradiated can be adjusted by the intensity of the lamp. For example, when the intensity is 10 mW / cm ² , the treatment can be performed for 5 to 10 minutes. If the transfer should be performed with an infrared lamp in a short time at a time, a photothermal conversion layer may be selectively inserted.

  When the energy source is heat, transfer can be performed by processing at a temperature of 60 to 80 ° C. for 10 to 30 minutes.

  When the energy source is pressure, it is preferable to further form a support layer on the side opposite to the patterned side of the soft polymer film layer that is patterned so that a uniform pressure is applied throughout the donor film. . The support layer is made of glass, polyethylene terephthalate, polycarbonate, polyester, polyethylene naphthalate, polyester sulfonate, polysulfonate, polyarylate, fluorinated polyimide, fluorinated resin, polyacryl, polyepoxy, polyethylene, polystyrene, polyacetate and polyimide. It may be any one selected from the group consisting of:

The pressure may be applied at a magnitude of 10 kPa to 100 mPa for 2 to 60 seconds. When electricity is used as an energy source, the applied current can be applied at a magnitude of 1 mA / cm ² to 10 A / cm ² for 1 minute to 1 hour.

  The metal layer may be a metal having a work function of 2.0 eV to 6.0 eV, and may have a two-layer structure including a first metal layer and a second metal layer. In the case of such a two-layer structure, the first metal layer attached to the soft polymer film layer has a high work function and does not react well with the polymer film layer. , Al, Ag, Au, Pd or Pt. The second metal layer attached to the first metal layer is preferably a metal having a low work function, and examples thereof include Ba, Ca, Mg, Cs, Li, and alloys between these and other metals. .

  When the layer to be transferred is a metal layer, the adhesive force between the metal and the organic material forming the acceptor film is greater than the adhesive force between the metal and the soft polymer film layer, so a little energy is added. However, the metal layer can be easily separated from the film layer.

  That is, when PDMS is used as a soft polymer film, the difference in adhesive force W can be expressed by the surface energy γ as follows.

When 1 is a soft polymer film, 2 is a metal, and 3 is a lower organic layer, the second term on the right side of the final formula is much smaller than the first term. This is because γ (metal) is much larger than γ (lower organic matter) and γ (PDMS). Therefore, the difference in surface energy between the lower organic layer and PDMS becomes equal to the difference in adhesion. In the case of PDMS, the surface energy is as low as 19.8 mJ / m ^2, and thus has a weaker binding force than the lower organic layer. When the lower organic substance is, for example, MEH-PPV [poly (2-methoxy-5- (2′-ethyl-hexyloxy) -1,4-phenylenevinylene)] which is a light-emitting substance, 28.0 mJ / m ² shows a large surface energy, so that if there is no external energy for a long time, the transfer is performed well due to the difference in binding force, and if external energy, that is, heat is applied at 80 ° C. for 20 minutes or more, The transfer time is faster.

  The organic layer, which is the transfer layer to be transferred by the donor film, includes a hole transport layer, a light emitting layer, and an electron transport layer, and an electron injection layer, a hole injection layer, an electron blocking layer, or a hole blocking layer as necessary. A layer may further be provided.

  1A and 1B are process diagrams showing a method of manufacturing a patterned organic EL element by transferring only a metal layer using a donor film for thin film transfer. This is an effective method particularly when a passive matrix type organic EL element is manufactured.

  In the step (a) of FIG. 1A, a metal layer 102a is deposited on the patterned soft polymer film layer 101 to produce a donor film for thin film transfer. Next, in the step (b), the metal layer 102a of the donor film for thin film transfer is positioned so as to be in contact with the organic layer 103 laminated on the substrate 105 and the anode 104, and then heat, light, electricity and If one or more of the pressures are applied to remove the donor film, the metal layer 102a is transferred to the organic layer 103 to complete the organic EL element, as shown in (c).

  FIG. 1B is a view illustrating an embodiment in which a transfer is performed by applying pressure, and is opposite to the patterned side of the soft polymer film layer 101 so that the pressure is uniformly applied to the donor film for thin film transfer. Except for forming the support layer 100 on this side, the same process as in FIG. 1A is performed.

  In the case of manufacturing an organic EL device by transferring only an organic layer using a donor film for thin film transfer, a step of forming an anode on a substrate, and a step of forming a first organic layer on the anode, A second organic layer of a donor film for thin film transfer comprising: a soft polymer film layer patterned in a concavo-convex pattern on the first organic layer; and a second organic layer formed on the polymer film layer. Forming the second organic layer patterned by applying one or more of heat, light, electricity and pressure to the first organic layer after the contact, and the second organic layer patterned And forming a cathode by forming a metal layer on the convex surface.

  After the patterned second organic layer is transferred to the first organic layer, a metal layer is deposited on the second organic layer to form a cathode. Examples of the vapor deposition method include a thermal vapor deposition method, an electron beam vapor deposition method, and sputtering. In this case as well, one or two metal layers can be formed.

  The second organic layer of the donor film and the first organic layer where transfer occurs may include an electron transport layer, a light emitting layer, and a hole transport layer, and an electron injection layer, a hole injection layer, and an electron blocking layer as necessary. A layer, a hole blocking layer.

  2A and 2B are process diagrams showing a method of manufacturing a patterned organic EL element by transferring only an organic layer using a donor film for thin film transfer.

  In step (a) of FIG. 2A, a second organic layer 202b is formed on the patterned soft polymer film layer 201 to produce a thin film transfer donor film. Next, in step (b), the second organic layer 202b of the donor film for thin film transfer is positioned so as to contact the substrate 205 and the first organic layer 203 laminated on the anode 204, and then heat, When one or more of light, electricity, and pressure are applied to remove the donor film, the second organic layer 202b is transferred to the first organic layer 203 as shown in (c). Thereafter, in step (d), a metal layer 202a is deposited on the patterned second organic layer 202b to form a cathode, thereby completing an organic EL element.

  FIG. 2B is a diagram illustrating an embodiment in which transfer is performed by applying pressure, and is opposite to the patterned side of the soft polymer film layer 201 so that the pressure is uniformly applied to the donor film for thin film transfer. Except for forming the support layer 200 on this side, the same process as in FIG. 2A is performed.

  When an organic EL device is manufactured by transferring both a metal layer and an organic layer using a donor film for thin film transfer, a step of forming an anode on the substrate and a first organic layer on the anode are formed. A soft polymer film layer patterned in a concavo-convex pattern on the first organic layer, a metal layer formed on the polymer film layer, and a second organic layer formed on the metal layer The metal layer and the second organic layer are transferred to the first organic layer by applying one or more of heat, light, electricity and pressure after contacting the second organic layer of the donor film for thin film transfer comprising And forming the patterned second organic layer and the cathode.

  FIG. 3 is a process diagram showing a method of manufacturing a patterned organic EL element by transferring a metal layer and a second organic layer together using a donor film for thin film transfer.

  In step (a) of FIG. 3, a first metal layer 302a ′, a second metal layer 302a ″, and a second organic layer 302b are sequentially formed on the patterned soft polymer film layer 301 to transfer a thin film. Next, in step (b), the second organic layer 302b of the donor film for thin film transfer is positioned so as to be in contact with the first organic layer 303 laminated on the substrate 305 and the anode 304. After that, if one or more of heat, light, electricity and pressure is applied and the donor film is removed, the metal layer 302a and the second organic layer 302b are attached to the first organic layer 303 as shown in FIG. The patterned organic EL element is completed by being transferred.

  The second organic layer of the donor film and the first organic layer where transfer occurs may include an electron transport layer, a light emitting layer, and a hole transport layer, and an electron injection layer, a hole injection layer, and an electron blocking layer as necessary. A layer, a hole blocking layer.

  The donor film for thin film transfer used in the method of the present invention comprises a step of producing a soft polymer film layer, preferably a soft polymer film layer having a glass transition temperature of room temperature or lower, and the polymer film layer. And a step of forming a metal layer, a second organic layer, or a metal layer and a second organic layer thereon.

  When the soft polymer film layer further includes a support layer, after depositing a metal layer, a second organic layer or a metal layer and a second organic layer on the polymer film layer, the polymer film layer A support layer can be deposited on the side opposite the side on which the layer is formed.

  The patterned soft polymer film layer can be manufactured by the following method. Prepare a master consisting of wafers. The master has a predetermined uneven pattern. Thereafter, a precursor solution for forming a soft polymer film is prepared. The precursor solution for forming the polymer film is easily purchased from various chemical manufacturers. For example, when obtaining polydimethylsiloxane (PDMS), Sylgard 184 of Dow Chemical Inc. Series can be used. After pouring the prepared polymer film-forming solution onto the master, the solution is heated to an appropriate temperature and time (for example, in the case of PDMS, from room temperature to 100 ° C. for 1 hour to 24 hours, preferably 60 ° C. to 80 ° C. Cured at 1 ° C. for 1 to 3 hours to form a patterned polymer film layer. Then, the patterned polymer film layer is removed from the master.

  A metal layer or a second organic layer is deposited on the entire surface of the patterned polymer film layer manufactured as described above. At this time, it is preferable to use a vertical vapor deposition method so that it is not vapor-deposited on the side surface. There are no particular restrictions on the deposition process, and various deposition methods such as sputtering, electron beam deposition, and thermal deposition can be used.

  The anode constituting the organic EL device according to the present invention may be any one selected from the group consisting of ITO, IZO, ITZO, Au, Ag, Al, polythiophene, polypyrrole, and polyaniline derivatives.

  In addition, the cathode constituting the organic EL device according to the present invention may be composed of one layer or two layers made of a metal having a work function of 2.0 eV to 6.0 eV.

  The hole injection layer in the organic layer constituting the organic EL device according to the present invention is a conductive polymer such as PEDOT (poly-3,4-ethylenedithiothiophene), polypyrrole, polyaniline, or has a HOMO value of 4. It may be an organic substance that is 5 to 6.0 eV. The light-emitting layer is a high molecular weight substance including polyfluorene, spirofluorene, polyphenylene, polyphenylene vinylene, polythiophene, polysulfone, polyquinoline, polyquinoxaline, polyphenoxazine, polythiazine and derivatives thereof, or a low molecular weight of 10,000 or less. It can be a molecular substance. The hole transport layer may be an organic low molecular weight material or a high molecular weight material including a group having a hole transport function such as carbazole or arylamine. The electron transport layer may be an organic low molecular weight material or a high molecular weight material including a functional group having an electron transport function such as quinoline, quinoxaline, and a metal complex fluorescent material. The electron injection layer can be made of a metal halide, a metal oxide, or the like.

  Hereinafter, the present invention will be described in more detail through examples.

<Example 1>
<Manufacture of donor film for thin film transfer (when transfer layer is only metal layer)>
Sylgard 184A and Sylgard 184B (manufactured by Dow Corning Inc.) were mixed at a weight ratio of 10: 1 in a stirring vessel. The PDMS formation solution obtained from this was poured onto a master made of a wafer prepared in advance. The master has a striped pattern. After removing bubbles in the PDMS forming solution poured on the master using a vacuum pump, the PDMS forming solution is cured in an oven at 60 ° C. to 80 ° C., and then the master is removed. A PDMS film layer was obtained.

Au was deposited on the patterned surface of the PDMS film layer obtained above by electron beam evaporation under a reduced pressure of 1 × 10 ⁻⁷ torr (1.33 × 10 ⁻⁵ Pa) to a thickness of 20 nm.

<Manufacture of patterned organic EL elements>
A glass substrate as a substrate and a first electrode and 15 Ω / cm ² (1200 mm) ITO was cut into a size of 50 mm × 50 mm × 0.7 mm, washed with sonic alcohol and pure water for 5 minutes each, and then 30 It was used after UV and ozone cleaning for a minute. PFB (a hole transport material manufactured by Dow Chemical Co.) was spin coated on the ITO electrode to form a 10 nm thick hole transport layer. An electron transport layer made of aluminaquinone (Alq ₃ ) is formed on the light emitting layer after forming a light emitting layer having a thickness of 70 nm with a spirofluorene-based light emitting polymer as a blue light emitting material on the hole transport layer. Was deposited to a thickness of 30 nm. After making the convex part of the donor film manufactured above contact, it was transferred by irradiating with an IR lamp for 10 minutes, thereby forming a patterned cathode to complete an organic EL device.

<Example 2>
<Manufacture of donor film for thin film transfer (when transfer layer is only organic layer)>
Sylgard 184A and Sylgard 184B (manufactured by Dow Corning Inc.) were mixed at a weight ratio of 10: 1 in a stirring vessel. The PDMS formation solution obtained from this was poured onto a master made of a wafer prepared in advance. The master has a striped pattern. After removing bubbles in the PDMS formation solution poured onto the master using a vacuum pump, the PDMS formation solution is cured at 60 ° C. to 80 ° C. in an oven, and then the master is removed. A PDMS film layer was obtained.

Alq ₃ was deposited at 30 nm under reduced pressure of 1 × 10 ⁻⁷ torr (1.33 × 10 ⁻⁵ Pa) as a second organic layer forming an electron transport layer on the patterned surface of the PDMS film layer obtained above. It was.

<Manufacture of patterned organic EL elements>
A substrate and a glass substrate as a first electrode and 15 Ω / cm ² (1200 mm) ITO were cut into a size of 50 mm × 50 mm × 0.7 mm, and cleaned with sonic alcohol and pure water for 5 minutes each, followed by 30 It was used after UV and ozone cleaning for a minute. A PFB (a hole transport material manufactured by Dow Chemical) was spin coated on the ITO electrode to form a 10 nm thick hole transport layer. A light emitting layer having a thickness of 70 nm was formed on the hole transport layer with a spirofluorene-based light emitting polymer that is a blue light emitting material. After making the convex part of the donor film manufactured above contact, it transferred by irradiating with an IR lamp for 10 minutes to form a patterned electron transport layer. An organic EL device was completed by depositing metal Ca / Al to a thickness of 5 nm / 250 nm on the electron transport layer to form a cathode.

<Example 3>
<Manufacture of donor film for thin film transfer (when transfer layer is metal layer and organic layer)>
Sylgard 184A and Sylgard 184B (manufactured by Dow Corning Inc.) were mixed at a weight ratio of 10: 1 in a stirring vessel. The PDMS formation solution obtained from this was poured onto a master made of a wafer prepared in advance. The master has a striped pattern. After removing bubbles in the PDMS formation solution poured onto the master using a vacuum pump, the PDMS formation solution is cured at 60 ° C. to 80 ° C. in an oven, and then the master is removed. A PDMS film layer was obtained.

On the patterned surface of the PDMS film layer obtained above, metal Au was evaporated to 20 nm by electron beam evaporation. Thereafter, Ca was vapor-deposited to 5 nm by thermal evaporation, and Alq ₃ was vapor-deposited to 5 nm on the second organic layer serving as an electron transport layer on the vapor-deposited metal layer.

<Manufacture of patterned organic EL element 1 (when light energy is used)>
A glass substrate as a substrate and a first electrode and 15 Ω / cm ² (1200 mm) ITO was cut into a size of 50 mm × 50 mm × 0.7 mm, washed with sonic alcohol and pure water for 5 minutes each, and then 30 It was used after being washed with UV and ozone for a minute. A 10 nm thick hole transport layer was formed by spin coating PFB (a hole transport material manufactured by Dow Chemical Co.) on the ITO electrode. After forming a light emitting layer having a thickness of 70 nm with a spirofluorene-based light emitting polymer as a blue light emitting material on the hole transport layer, the convex portion of the donor film manufactured as described above is brought into contact with the IR lamp. The organic EL device was completed by forming a patterned cathode and an electron transport layer by transferring by irradiation for 10 minutes.

<Manufacture of patterned organic EL elements 2 (when electric energy is used)>
A glass substrate as a substrate and a first electrode and 15 Ω / cm ² (1200 mm) ITO was cut into a size of 50 mm × 50 mm × 0.7 mm, washed with sonic alcohol and pure water for 5 minutes each, and then 30 It was used after being washed with UV and ozone for a minute. A PFB (a hole transport material manufactured by Dow Chemical) was spin coated on the ITO electrode to form a 10 nm thick hole transport layer. After forming a light emitting layer having a thickness of 70 nm with a spirofluorene-based light emitting polymer, which is a blue light emitting material, on the hole transport layer, after contacting a convex portion of the donor film manufactured above, an anode and A ground was connected to the cathode, and a current of 1 A / cm ² was applied for 30 minutes to perform transfer, whereby a patterned cathode and an electron transport layer were formed to complete an organic EL device.

<Manufacture of patterned organic EL element 3 (when pressure is used)>
A glass substrate as a substrate and a first electrode and 15 Ω / cm ² (1200 mm) ITO were cut into a size of 50 mm × 50 mm × 0.7 mm, washed with ultrasonic waves in isopropyl alcohol and pure water for 5 minutes each, and then 30 It was used after being washed with UV and ozone for a minute. A 10 nm thick hole transport layer was formed by spin coating PFB (a hole transport material manufactured by Dow Chemical Co.) on the ITO electrode. After forming a light emitting layer having a thickness of 70 nm with a spirofluorene-based light emitting polymer, which is a blue light emitting material, on the hole transport layer, a glass support is attached to the donor film manufactured as described above to form a convex portion. After making contact with the lower side, transfer was performed by applying a pressure of 150 kPa for 15 seconds to form a patterned cathode and an electron transport layer, thereby completing an organic EL device.

<Comparative Example 1>
<Manufacture of patterned organic EL elements>
After cutting a glass substrate and 15 Ω / cm ² (1200 ° C.) ITO as a substrate and a first electrode into a size of 50 mm × 50 mm × 0.7 mm and washing with ultrasonic waves in isopropyl alcohol and pure water for 5 minutes each, It was used after being washed with UV and ozone for 30 minutes. A 10 nm thick hole transport layer was formed by spin coating PFB (a hole transport material manufactured by Dow Chemical Co.) on the ITO electrode. A light emitting layer having a thickness of 70 nm is formed on the hole transporting layer with a spirofluorene-based light emitting polymer as a blue light emitting material, and then an electron transporting layer made of Alq ₃ is formed on the light emitting layer with a thickness of 30 nm. Vapor deposited. An organic EL device was completed by depositing 20 nm of Au by thermal evaporation under reduced pressure of 1 × 10 ⁻⁷ torr (1.33 × 10 ⁻⁵ Pa).

<Evaluation test 1>
In order to test the performance of the organic EL device manufactured by the method according to the present invention, the current and emission intensity according to the electric field strength were measured for the organic EL device manufactured in Example 1, and the results are shown in FIG. Shown in

  As shown in FIG. 4, the organic EL device manufactured by the manufacturing method of the present invention was formed well by expressing the current-electric field characteristics and the light intensity-electric field characteristics expressed by the diodes. I understand.

<Evaluation Test 2>
In order to test the performance of the organic EL device manufactured by the method according to the present invention, the efficiency (luminance / current) was measured with the Minolta CS1000 and Keithley 236 for the organic EL device manufactured in Example 1, and The efficiency was measured in the same manner for the organic EL device produced in Comparative Example 1. As a result of measurement, the efficiency of 0.05 cd / A was shown in Example 1, whereas the efficiency in Comparative Example 1 was 0.01 cd / A, which further improved the device manufacturing method according to the present invention. You can see that

  The present invention can be suitably applied to technical fields related to organic electroluminescence.

1 is a view showing an embodiment of a method for manufacturing an organic EL element according to the present invention, in which transfer is performed by heat. 1 is a diagram illustrating an embodiment of a method for manufacturing an organic EL element according to the present invention, in which transfer is performed by pressure. It is drawing which shows the other implementation example of the manufacturing method of the organic EL element concerning this invention, Comprising: It is a case where it transfers with a heat | fever. It is drawing which shows the other implementation example of the manufacturing method of the organic EL element which concerns on this invention, Comprising: It is a case where it transfers by pressure. It is drawing which shows the other implementation example of the manufacturing method of the organic EL element concerning this invention. It is drawing which shows the electric current and light intensity of the organic EL element which concern on this invention.

Explanation of symbols

101, 201, 301 soft polymer film layer,
100, 200 support layer,
102a, 202a, 302a metal layer,
103, 103a organic layer,
203, 303 first organic layer,
202b, 302b second organic layer,
104, 204, 304 anode,
105, 205, 305 substrate,
302a ′ first metal layer,
302a "second metal layer.

Claims (21)

Forming an anode on a substrate;
Forming an organic layer on the anode;
After contacting the metal layer of the donor film for thin film transfer comprising the soft polymer film layer patterned in an uneven shape on the organic layer, and the metal layer formed on the polymer film layer, heat, Applying one or more of light, electricity and pressure to transfer the metal layer to the organic layer to form a patterned cathode;
The manufacturing method of the organic electroluminescent element containing this.   The manufacturing method according to claim 1, wherein the organic layer includes a hole transport layer, a light emitting layer, and an electron transport layer.   The soft polymer film layer has a glass transition temperature of room temperature or lower, and is selected from the group consisting of silicon elastomer, polybutadiene, nitrile rubber, acrylic rubber, butyl rubber, polyisoprene, and styrene-butadiene copolymer. It is the above, The manufacturing method of Claim 1 characterized by the above-mentioned.   The manufacturing method according to claim 3, wherein the silicone elastomer is polydimethylsiloxane.   The manufacturing method according to claim 1, wherein the soft polymer film layer further includes a support layer on a surface opposite to the patterned side.   The support layer is made of glass, polyethylene terephthalate, polycarbonate, polyester, polyethylene naphthalate, polyester sulfonate, polysulfonate, polyarylate, fluorinated polyimide, fluorinated resin, polyacryl, polyepoxy, polyethylene, polystyrene, polyacetate and polyimide. The manufacturing method according to claim 5, wherein the method is any one selected from the group consisting of: Forming an anode on a substrate;
Forming a first organic layer on the anode;
Contacting the second organic layer of a donor film for thin film transfer comprising a soft polymer film layer patterned in a concavo-convex pattern and a second organic layer formed on the polymer film layer on the first organic layer And then applying one or more of heat, light, electricity and pressure to transfer the second organic layer to the first organic layer to form a patterned second organic layer;
Depositing a metal layer on the patterned second organic layer to form a cathode, and a method for manufacturing an organic electroluminescent device.   The method according to claim 7, wherein the first organic layer and the second organic layer include a hole transport layer, a light emitting layer, and an electron transport layer.   The soft polymer film layer has a glass transition temperature of room temperature or lower, and is selected from the group consisting of silicon elastomer, polybutadiene, nitrile rubber, acrylic rubber, butyl rubber, polyisoprene, and styrene-butadiene copolymer. It is the above, The manufacturing method of Claim 7 characterized by the above-mentioned.   The method according to claim 9, wherein the silicon-based elastomer is polydimethylsiloxane.   The manufacturing method according to claim 7, wherein the soft polymer film layer further includes a support layer on a surface opposite to the patterned side.   The support layer is made of glass, polyethylene terephthalate, polycarbonate, polyester, polyethylene naphthalate, polyester sulfonate, polysulfonate, polyarylate, fluorinated polyimide, fluorinated resin, polyacryl, polyepoxy, polyethylene, polystyrene, polyacetate and polyimide. The manufacturing method according to claim 7, wherein the method is any one selected from the group consisting of: Forming an anode on a substrate;
Forming a first organic layer on the anode;
Thin film transfer comprising a soft polymer film layer patterned in a concavo-convex pattern on the first organic layer, a metal layer formed on the polymer film layer, and a second organic layer formed on the metal layer After bringing the second organic layer of the donor film into contact, patterning is performed by transferring the metal layer and the second organic layer to the first organic layer by applying one or more of heat, light, electricity, and pressure. Forming the formed second organic layer and cathode;
A method for producing an organic electroluminescent device comprising   The method according to claim 13, wherein the first organic layer and the second organic layer include a hole transport layer, a light emitting layer, and an electron transport layer.   The soft polymer film layer has a glass transition temperature of room temperature or lower, and is selected from the group consisting of silicon elastomer, polybutadiene, nitrile rubber, acrylic rubber, butyl rubber, polyisoprene, and styrene-butadiene copolymer. It is the above, The manufacturing method of Claim 13 characterized by the above-mentioned.   The manufacturing method according to claim 15, wherein the silicone elastomer is polydimethylsiloxane.   The manufacturing method according to claim 13, wherein the soft polymer film layer further includes a support layer on a surface opposite to the patterned side.   The support layer is made of glass, polyethylene terephthalate, polycarbonate, polyester, polyethylene naphthalate, polyester sulfonate, polysulfonate, polyarylate, fluorinated polyimide, fluorinated resin, polyacryl, polyepoxy, polyethylene, polystyrene, polyacetate and polyimide. The manufacturing method according to claim 13, which is any one selected from the group consisting of:   An organic electroluminescent device comprising an anode, an organic layer, and a cathode, and produced by the production method according to claim 1.   The organic electroluminescent device according to claim 19, wherein the anode is any one selected from the group consisting of ITO, IZO, ITZO, Au, Ag, Al, polythiophene, polypyrrole, and polyaniline derivatives. .   The organic electroluminescent device according to claim 19, wherein the cathode comprises one layer or two layers made of a metal having a work function of 2.0 eV to 6.0 eV.